Process of reacting a polyisocyanate with a compound having active hydrogen using a tertiary amine n-oxide and hydrogen peroxide catalyst mixture



United States Patent Ofiice 3,173,897 Patented Mar. 16, 1965 Thisinvention relates to a process of reacting organic polyisocyanatecompounds with water or a mixture of Water and organic hydroxy compoundsand more paniculerly to such a process wherein a catalyst consisting ofa tertiary amine N-oxide in combination with hydrogen peroxide isemployed.

It is an object of the present invention to provide a novel chemicalprocess. A further object is to provide an improved process for reactingan organic polyisocyanate v compound with water or a mixture of waterand an organic hydroxy compound. A still further object is to provide anew process for catalyzing the reaction of an organic polyisocyanatecompound with water or a mixture of water and an organic hydroxycompound wherein the catalyst consists of a tertiary amine N-oxide incombination with hydrogen peroxide. Other objects will appearhereinafter.

These and other objects of this invention are accomplished by theprocess of reacting an organic polyisocyanate with water or a mixture ofwater and an organic compound having at least one alcoholic hydroxylgroup, with the proviso that the reaction be carried out in contact withaqueous hydrogen peroxide and a tertiary amine N-oxide having noisocyanate reactable suhstitucnts, said amine N-oxide being selectedfrom the group consisting of tertiary amine l -o1-rides having onlyaliphatic carbon atoms adjacently attached to the nitrogen atoms thereofand N-oxides of organic compounds having a pyridine nucleus. Thereaction of water or a mixture of water and an organic hydroxy compoundwith an organic polyisocyanate compound is well-known. Also it is knownto employ tertiary amines to catalyze this reaction. Similarly, the useof tertiary amine N-oxides to catalyze this reaction is described andclaimed in our copending application Serial No. 63,966, filed of eventla e herewith. It has now been found that an unexpected synergisticeffect occurs when aqueous hydrogen peroxide is used in combination withthe tertiary amine N-oxide to catalyze this reaction. It is believedthat this discovery is quite unexpected in view of the fact that aqueoushydrogen peroxide itself exhibits no significant catalytic activity forthis reaction; however, when it is used in combination with the tertiaryamine N-oxide the catalytic activity of the combination is significantlygreater than that of the tertiary amine per se. Also, the use of aqueoushydrogen peroxide in combination with the tertiary amine N-oxide resuitsgreater catalytic activity than the use or" the tertiary amine N-oxideper se.

Any organic polyisocyaria e compound including aromatic, aliphat c andcycloaliphatic types may be em ployed in the present invention. Thesecompounds may contain two or more isocyanate radicals. Mixtures of thesepolyisocyanate compounds can be employed when desired.

Representative polyisocyanate compounds includetoluene-2,4-diisocyanate, 1,-hexamethylenediisocyanate,1,4tetramethylenediisocyanate, 1,10-decarnethylenediisocyanate,1,S-naphthalenediisccyanate,

cumene-2,4-diisocyanate, 4-methoxy-1,3-phenylenediisocyanate,4-chloro-1,3-phenylenediisocyanate, 4-b-romo-1,3-phenylenediisocyanate,4-ethoxy-l,3-phenylenediisocyanatc, 2,4'-diisocyanatodiphenylether,5,6-dimethyl-1,3-phenylcnediisccyanate, 2,4-dimethyl-1,3-

phenylenediisocyan-ate, 4-,4-diisocyanatodiphenylether,benzidinediisocyanate, 4,6-dimethyl-1,3-phenylenediisocyanate, 9,IO-anthracenediisocyanatc, 4,4'-diisocyanatodibenzyl,3,3-dimethyl-4,4'-diisocyanatodiphenylmethane,2,6-dimethyl-'4,4'-diisocyanatodiphenyl, 2,4-diisocyanatostilbene,3,3'-dimethyl-4,4-diisocyanatodiphenyl,3,3-din1ethoxy-4,4'-diisocyanatodiphenyl, 1,4-anthracencdiisocyanate,2,5-fluorenediisocyanate, 1,8-naphthalenediisocyanate,2,6-diisocyanatobenzfuran, 2,4,o-toiuenetriisocyanate, and2,4,4'-triisocyanatodiphenylether.

Other representative organic polyisocyanates include the polyisocyanateswhich are described in U.S. 2,683,730; the phenyl indane diisocyanateswhich are described in US. 2,855,385; the organic diisocyanatcs whichare described in US. 2,292,443; and the organic triisocyanates which aredescribed in US. 2,929,794.

The organic isocyanate compounds which can be used also include theisocyanate-ternnnated reaction products of a molar excess of any of theabove described polyisocyanates with any of the polyhydroxy compoundsdescribed below. A representative example is an isocyanate terminatedpolyalkyleneether polyurethane which is described in British Patent733,624.

Any organic compound having at least one alcoholic hydroxyl group as itssole isocyanate reactable functionality can be employed in combinationwith water for reaction with the organic polyisocyanate compound.Mixtures of two or more or" these hydroxy compounds can be employed whendesired. Since aqueous hydrogen peroxide is employed as part or thecatalyst combination, the water associated with the hydrogen peroxide isalways present as a reactant. Representative examples of suitablealcohols can be found on pp. 226-228 of The Systematic Identification ofOrganic Compounds, R. L. Shriner and R. C. Fuson, 3rd ed., 1948, JohnWiley & Sons, Inc., New York; Synthetic Organic Chemistry, R. B. Wagnerand H. D. Zook, 1953, .tohn Wiley & Sons, Inc., New York, Table 11 (pp.182-193) and Tables 13 and 14 (pp. 197-202). Representative examples oflow molecular weight dihydroxy compounds can be found on pp. 193-196 ofSynthetic Organic Chemistry, supra. Further examples include alkyleneoxide modified polyols such as diethylene glycol,(Z-hydroxyethoxy)-1-pr0panol, 4- (Z-hydroxyethoxy) -1-butanol,S-(Z-hydroxyethoxy) -1- pentanol, 3-(2-hydroxypropoxy) 1 propanol,4-(2-hydroxypropoxy) 1 butanol, 5 (2 hydroXypropoXy)-1- pentanol,1-(2-hydroxyethoxy)-2-butano1, I-(Z-hydroxyethoxy)-2-pentanol, 1 (2hydroxyethoxy) 2 hexanol, 1- Z-hydroxyethoxy) -2-octanol, 1-(Z-hydroxypropoxy) -2- butanol, 1-(2-hydroxypropoxy) 2 propanol,1-(2-hydroxypropoxy) -2-hexanol, 1- 2-hydroxypropoxy) -2-octanol,3-(2-hydroxyethoxy)-1,2-propanediol, 3-(2-hydroxypropoxy) 1,2propanediol, 6 (2-hydroxycthoxy)-1,2- hexanediol, o-(2-hydroxypropony)1,2 hexanediol and 2,4- dimethyl 2 (2 hydroxyethoxy)methylpentanediol1,5. Ethyienically unsaturated low molecular Weight diols may beemployed. These include 3-allyloxy 1,5 pcntanediol, 3 allyloxy 1,2propanediol,

amass? 2-allyloxyrnethyl-Z-methyl-1,3 propanediol, Z-methyl-Z- [(4pentenyloxy)methyl] 1,3 propanediol and 3-(0-propenylphenoxy)-1,2-propanediol; others are listed in US. 2,927,098,and 2,854,486. Representative examples of low molecular weight polyolshaving at least 3 hydroxyl groups include: glycerol, 1,2,6-hexanetriol,1,1,l-trimethylolpropane, 1,1,1-trimethylolethane, pentaerythritol,mannitol, galactitol, talitol, iditol, ailitol, altritol, gulitol,arabitol, ribitol, xylitol, lyxitol, erythritol, threitol,1,2,5,6-tetrahydroxyhexane, meso-inosi'tol, sucrose, glucose, galactose,mannose, fructose, xylose, arabinose, dihydroxyacetone,glueose-u-methyl-glucoside, 1,1,1-tris (2-hydroxyethoxy) methyl] ethane,and 1 ,l ,1- tris[(2 hydroxypropoxy)methyl]propane. Other examples areincluded in US. 2,917,468. The following classes are representative ofthe hydroxyl-terminated polymers which can be used in the presentinvention: the hydroxyl-terminated polyhydrocarbons which are describedin US. 2,877,212; the hydroxyl-terminated polytormals which aredescribed in US. 2,870,097; the

fatty acid triglycerides which are described in US. 2,833,730, and US.2,787,601; the hydroxyl-terminated polyesters which are described inU.S. 2,698,838; US. 2,921,915; US. 2,591,884; US. 2,866,762; US. 2,850,-476; U.S. 2,602,783; US. 2,729,618; US. 2,779,689; US. 2,811,493 and US.2,621,166; the hydroxymethylterminated perfluoromethylenes which aredescribed in U.S. 2,911,390 and US. 2,902,473; the polyalliyleneetherglycols which are described in 2,808,391 and British 773,624; thepolyalkylenearyleneether glycols which are described in US. 2,808,391;the polyalkyleneether triols which are described in U.S. 2,866,774;polyvinyl alcohol and cellulose.

The process of the present invention can be operated atsuperatmospheric, atmospheric or subatrnospheric pressure. Atmosphericpressure is preferred. The reaction is generally operated attemperatures ranging from about C. to about 100 C. Lower temperaturesare possible but the reaction rate is often too slow for convenience.Those skilled in the art can select a mixing temperature at which thereaction mixture is fluid enough to permit satisfactory stirring. If themixing temperature is too high, water may be lost throughvolatilization; in addition, the reaction may take place so rapidly thatadequate mixing and control are not attained. If desired, the reactionmay be carried out in an inert solvent. Representative solvents includetetrahydrofuran, o-dichlorobenzene, chlorobenz ene, xylene,methylisobutylketone, toluene and ethyl acetate. In general, any solventused should be free from isocyanate reactable substituents such asgroups bearing Zerewitinofiactive hydrogen atoms.

When the organic polyisocyanate is being reacted with water inaccordance with the present invention, the reactants and catalystcomponents can be mixed in any order. Thus, the tertiary amine N-oxideand the aqueous hydrogen peroxide can be mixed separately and theresulting mixture then added to the organic polyisocyanate or a mixtureof the organic polyisocyanate and water; the aqueous hydrogen peroxidecan be added to a mixture of tertiary amine N-oxide and organicpolyisocyanate, the tertiary amine N-oxide can be introduced into amixture of aqueous hydrogen peroxide and organic polyisocyanate; theaqueous hydrogen peroxide, the amine N-oxide and the polyisocyanate canbe simultaneously brought together. Since tertiary amine N- oxides areknown to catalyze the dimerization and trimerization of organicisocyanates, it is best not to add them to the organic polyisocyanatemuch in advance of the aqueous hydrogen peroxide when the organichydroxy compound is absent.

Additions can be made in any order when the organic polyisocyanate isbeing reacted with a mixture of the organic hydroxy compound and water.The catalyst components and the reactants can be brought togethersimultaneously. The catalyst components can be added, together orsequentially, to the organic hydroxy compound and the resulting mixture,in turn, can be introduced into the organic polyisocyanate. The catalystcomponents can be added, together or sequentially, to a mixture of theorganic hydroxy compound and the organic polyisocyanate. The catalystcomponents can be added, together or sequentially, to the polyisocyanateand the resulting mixture quickly contacted with the hydroxy compound.Since the isocyanate/ water reaction is strongly accelerated by thecatalyst combination, the addition of the hydroxy compound must not bedelayed.

The value of the catalyst concentration can range widely. Those skilledin the art can readily select proportions which will provide the'degreeof catalytic acceleration desired. in general. the greater the catalystconcentration, the greater the acceleration. About 0.01 to 1.0 mole oftertiary amine N-oxide will be used for every mole of NCO groups.Concentrations below 0.01 mole can be used, but the catalytic eliect isnot enough to be convenient for some purpose. Concentrations above about0.3-0.5 mole are usually unnecessary. When concentrations above 1.0 moleare used, the reaction rate may be inconveniently fast. The preferredconcentration ranges between about 0.1 to 0.3 mole. When tertiarydiamine N-oxides are used, the above proportions can, of course, behalved. The activity of any individual tertiary amine N-oxide willdetermine the proper amount to use for a particular application. Forevery mole of tertiary amine N-oxide about 0.1 to 20 moles of hydrogenperoxide is supplied. The catalytic activity of the tertiary amineN-oxide is increased when less than 0.1 mole of hydrogen peroxide ispresent, but the degree of improvement is not always entirelysatisfactory. There is no particular advantage in using more than about20 moles of hydrogen peroxide per mole of tertiary amine N-oxide. Thepreferred proportion ranges between about 0.1 to 1 mole. The strength ofthe aqueous hydrogen peroxide solution is not critical insofar as theoperation of the present invention is concerned. Representativesolutions which can be used contain 3% and 30% hydrogen peroxide byweight; the latter can be diluted to give solutions of intermediatestrength. The water consumed by the organic polyisocyanate can besupplied wholly or in part by the aqueous hydrogen peroxide solution.

Insofar as the operation of the present invention is concerned, thevalue of the molar ratios of NCG-groups/ water andNCO-groups/(water-PHO-groups) can vary widely. Those skilled in the artcan determine the proportions of reactants best suited for a particularpurpose. For example, when making foams by reacting polyisocyanates withwater, one often provides a molecule of water for every pair ofNCO-groups present.

The tertiary amine N-oxide may be prepared by reaction of the parenttertiary amine with hydrogen peroxide. In a representative procedure, awater-soluble tertiary amine is reacted at about 2530 C. with a 2-foldmolar excess of 10% aqueous hydrogen peroxide for about 48 hours.Completion of reaction is indicated by the disappearance of thecharacteristic amine odor. The residual hydrogen peroxide iscatalytically destroyed by agitation with ruthenium on carbon. Afterfiltering, the water is removed by distillation. The N-oxide therebyobtained is recrystallized from common solvents such as ethyl acetate orbenzene. When water-insoluble tertiary amines are employed, acetone canbe added to the water to effect solubilization.

Two classes of tertiary amine N-oxides may be employed in combinationwith the aqueous hydrogen peroxide. The first class includes N-oxides oftertiary amines having only aliphatic carbon atoms adjacently attachedto the nitrogen atom or atoms thereof. Although there are no aromaticgroups attached to the nitrogen atom, they may be present elsewhere inthe molecule. The second class includes N-oxides of organic compoundshaving a pyridine nucleus. These compounds may, if

desired, contain an N-oxide of a tertiary nitrogen atom of the typecharacteristic of the first class. All of these amine oxides are freefrom isocyanate-reactable substituents such as isocyanate groups,1,3-diazacyclobutane-2,4- dione groups, and groups bearingZerewitinofl-active hydrogen atoms such as primary amino groups,secondary amino groups, amido groups, carboxyl groups, hydroxyl groups,mercapto groups, ureido groups, urethaneo groups, and the like. Mixturesof two or more of these tertiary amine N-oxides may be employed.

Representative examples of types of amine N-oxides included Within thefirst class are the N-Oxides of tertiary alkylamines, tertiarycycloalkylamines, and N-alkyl piperidines, N-alkyl morpholines, and theN,N'-dioxides of N,N'-dialkylpiperazines, and N,N,N',N-tetraalkylalkylenediamines. In general, these tertiary amines have from about 3 to 21carbon atoms. Representative amine N- oxides are: dimethyldodecylamineN-oxide, dimethyltetradecylamine N-oxide, diethylhexadecylamine N-oxide,methylethyloctadecylamine N-oxide, trimethylamine N- oxide,diethylrnethylamine N-oxide, tri-n-propylarm'ne N- oxide,tri-n-butylamine N-oxidc, tri-n-arnylarnine N-oxide,

Example 1 The catalyst and Water were added at 30 C. to milliliters oftetrahydrofuran and the solution obtained was introduced into a l25-ml.Erlenmeyer flask agitated by a magnetic stirrer and fitted with a 2-holerubber stopper holding a glass burette and a gas outlet tube. Thereaction was started by introducing, from the burette, a 10 percent byWeight solution of tOlLIEIlE-Z-i-(liiSOCYEIIIEIIfi in tetrahydrofuran atC. The carbon dioxide generated by the isocyanateavater reaction whichresulted passed through the outlet tube (of glass) to a T-joint attachedto an F and M Model 119C gas chromatograph having a S-ft. column packedwith firebrick coated with Perkin Elmer silicone grease type (0); ahelium stream flowed into the other side of the T-joint at the rate of20 -cc./rnin. The height of the instrument chart tracing for carbondioxide at any instant was taken as a relative measure of the amount ofcarbon dioxide generated at that moment. The time required for thecarbon dioxide band to reach a maximum and the height of that maximumwere recorded for each run and provided a comparative measure ofcatalyst reactivity. Table I which follows shows the data obtained.

Table l i Moles of Moles of Moles 0t Moles of Maximum Minutes AmineN-Oxide i Amine H2O; TDI b H O Chart to Chart I N-Oxide Reading MaximumDimcthyloctadecylamine N-oxide 0. 0008 0.0035 0. 0035 11, 800 2. 5 0.0008 0. 0008 0. 0035 0. 0035 95, 200 2 0. 007 0. 007 1, 900 20 PyridineN oxide 0. 0035 0. 0035 8, 600 16 0. 0035 0. 0035 43, 000 7Diethylcyclohexylamino N oxide O. 0035 O. 0035 7, 200 E2 0. 0035 0. 0035102, 400 N-Ethylmorpholine N-oxide n 0. 0035 0. 0035 4, 800 24 Suppliedas a 30% aqueous solution. b TDI: toluene-ZA-diisoeyanate.1,6-11oxamethylenediisocyanate was used instead oftoluene-2,4-diisocyanate.

diethylisopropylamine N-oxide, dimethyl-n-butylamine N- oxide,dimethylcyclohexylamine N-oxide, N-methylpiperidine N-oxide,N-ethylpiperidine N-oxide, N-propylpiperidine N-oxide,N-isopropylpiperidine N-oxide, N-n-butylpiperidine N-oxide, l-isobutylpiperidine N-0xide, N- isoamylpiperidine N-oxide,N-methyl-3-is0propylpiperi dine N-oxide, 2-methyl-N,3-diethylpiperidineN-oxide, N- methylmorpholine N-oxide, N-ethylmorpholine N-oxide,N,N-dimethylpiperazine N,N'-dioxide, N,N'-diethylpiperazine NIT-dioxide,N,N'-dipropylpiperazine N,N-dioxide, N,N'-diisoamylpiperazineN,N-dioxide, triethylenediarnine N,N-dioxide,N,N,N',N-tetramethyltrimethylenediamine N,N-dioxide,N,N,N,N'-tetraethyltrimethylenediamine N,N-dioxide,N,N,N',N'-tetramethyltetramethylcnediamine N,N-dioxide, and N,N,ll,N'-tetrame thylhexamethylenediamine N,N-dioxide.

Representative examples of types of amine N-oxides included Within thesecond class are pyridine N-oxides, quinoline N-oxides, and isoquinolineN-oxides. In general, these amines have from about 5 to 18 carbon atoms.Representative amine N-oxides are: pyridine N-oxide, 3-chloropyridineN-oxide, 3,5-dibromopyridine N-oxide, 4-methylpyridine N-oxide,3-ethyl-pyridine N-oxide, 2- methylpyridine N-oxide,4-tert-butylpyridine N-oxide, 3- phenylpyridine N-oxide,S-(p-isopropyl)benzylpyridine N-oxide, 4-p-isopropylphenethylpyridineN-oxide, 4-pmethoxyphenethylpyridine N-oxide, 3-benzhydrylpyridineN-oxide, quinoline N-oxide, S-chloroquinoline N-oxide, 4-brornoquinolineN-oxide, 3-methylquinoline N-oxide, 4-ethylquinoliue N-oxide,7-isopropylquinoline N-oxide, 5,6-benzoquinoline N-oxide,6-chloro-4-methylquinoline N-oxide, isoquinoline N-oxide, 8chloroisoquinoline N- oxide, 4-bromoisoquinoliue 'N-oxide, ando-methylisoquinoline N-oxide.

The following examples will better illustrate the nature of the presentinvention; however, the invention is not intended to be limited to theseexamples. Parts are by weight unless otherwise indicated.

As many widely different embodiments of this invention may be madewithout departing from the spirit and scope thereof, it is to beunderstood that this invention is not limited to the specificembodiments thereof except as defined in the appended claims.

What is claimed is:

1. In the process of reacting an orgauiic polyisocyanate compound with amaterial selected from the group consisting of Water and a mixture ofWater with an organic compound having at least one alcoholic hydroxylgroup as its sole isocyanate reactable functionality, the improvementcomprising carrying out the reaction in contact with a catalytic amountof a catalyst consisting of aqueous hydrogen peroxide and a tertiaryamine N-oxide having no isocyanate-reactabie substituents said amineN-oxide being selected from the group consisting of tertiary amineN-oxides having only aliphatic carbon atoms adjacently attached to thenitrogen atoms thereof and N-oxides of organic compounds having apyridine nucleus.

2. A process according to claim 1 wherein the organic poly-isocyanate istoluene-2,4-diisocyanate.

3. A process according to claim 2 wherein the organic compound having atleast one alcoholic hydroxyl group is a polyalkyleneether polyol.

4. A process according to claim 2 wherein the organic compound having atleast one alcoholic hydroxyl group is a polyester polyol.

5. A process according to claim 3 wherein the polyalkyleneether polyolis a polypropyleneether glycol.

6. A process according to claim 3 wherein the polyalkyleneether polyolis a polypropyleneether triol.

7. A process according to claim 1 wherein the tertiary amine N-oxide isN-ethylrnorpholine N-oxide.

8. A process according to claim 1 wherein the ratio of hydrogen peroxideto tertiary amine N-oxide ranges from 0.1 to 1.0 mole of hydrogenperoxide per mole of tertiary amine l -oxide.

9. A process according to claim 8 wherein the concentration of tertiaryamine 1 -oXide ranges from 0.1 to 0.3 mole per mole of. isocyanategroups.

'10. A process according to claim 1 wherein the tertiary amine N-oxide.is diethylcyclohexyarnine N-oxide.

11. A process according to claim 1 wherein the tertiary amine N-oxide isN-ethylmorpholine N-onide.

12. In the process of reacting an organic polyisocyanate compound withwater, the improvement comprising carrying out the reaction in contactwith a catalytic amount of a catalyst consisting of aqueous hydrogenperoxide and a tertiary amine N-oxide having no isocyanate-reactablesubstitutents, said amine N-oxide being selected from the groupconsisting of tertiary amine N-oxides having only aliphatic carbon atomsadjacently attached to the nitrogen atoms thereof and N-oxides oforganic compounds having a pyridine nucleus.

13. In the process of reacting toluene-2-4-diisocyanate with water, theimprovement comprising carrying out the reaction in contact with acatalytic amount of a catalyst consisting oi aqueous hydrogen peroxideand a tertiary amine N-oxide having no isocyanate-reactablesubstituents, said amine N-oxide being selected from the groupconsisting of tertiary amine N-oxides having only aliphatic car-honatoms adjacently attached to the nitrogen atoms thereof and N-oXides oforganic compounds having a 2% pyridine nucleus, said hydrogen peroxidebeing supplied in the proportion of at least 0.1 mole per mole of saidamine N-oxide.

14. In the process of reacting 1,6-hexamethylcne-diisocyanate withWater, the improvement comprising carrying out the reaction in contactwith a catalytic amount of a catalyst consisting of aqueous hydrogenperoxide and a tertiary amine N-oxide having no isocyanate-reactablesubstituents, said amine N-oxide being selected from the groupconsisting of tertiary amine N-oxides having only aliphatic carbon atomsadjacently attached to the nitrogen atoms thereof and N-oxides oforganic compounds having a pyridine nucleus, said hydrogen peroxidebeing supplied in the proportion of at least 0.1 mole per mole of saidamine N-oXide.

References Cited in the file of this patent UNITED STATES PATENTS2,740,743 Pace Apr. 3, 1956 2,879,250 Eisenmann et al Mar. 24, 19592,894,919 Simon et al July 14, 1959 2,977,330 Brower Mar. 28, 1961FQREIGN PATENTS 748,697 Great Britain May 9, 1956

1. IN THE PROCESS OF REACTING AN ORGANIC POLYISOCYANATE COMPOUND WITH AMATERIAL SELECTED FROM THE GROUP CONSISTING OF WATER AND A MIXTURE OFWATER WITH AN ORGANIC COMPOUND HAVING AT LEAST ONE ALCOHOLIC HYDROXYLGROUP AS ITS SOLE ISOCYANATE REACTABLE FUNCTIONALITY, THE IMPROVEMENTCOMPRISING CARRYING OUT THE REACTION IN CONTACT WITH A CATALYTIC AMOUNTOF A CATALYST CONSISTING OF AQUEOUS HYDROGEN PEROXIDE AND A TERTIARYAMINE N-OXIDE HAVING NO ISOCYANATE-REACTABLE SUBSTITUENTS SAID AMINEN-OXIDE BEING SELECTED FROMA THE GROUP CONSISTING OF TERTIARY AMINEN-OXIDES HAVING ONLY ALIPHATIC CARBON ATOMS ADJACENTLY ATTACHED TO THENITROGEN ATOMS THEREOF AND N-OXIDES OF ORGANIC COMPOUNDS HAVING APYRIDINE NUCLEUS.